Orbital Nature of Carboionic Monoradicals Made from Diradicals.

The electronic, optical, and solid state properties of a series of monoradicals, anions and cations obtained from starting neutral diradicals have been studied. Diradicals based on s-indacene and indenoacenes, with benzothiophenes fused and in different orientations, feature a varying degree of diradical character in the neutral state, which is here related with the properties of the radical redox forms. The analysis of their optical features in the polymethine monoradicals has been carried out in the framework of the molecular orbital and valence bond theories. Electronic UV-Vis-NIR absorption, X-ray solid-state diffraction and quantum chemical calculations have been carried out. Studies of the different positive-/negative-charged species, both residing in the same skeletal π-conjugated backbone, are rare for organic molecules. The key factor for the dual stabilization is the presence of the starting diradical character that enables to indistinctively accommodate a pseudo-hole and a pseudo-electron defect with certainly small reorganization energies for ambipolar charge transport.

Boron-Doped Pentacenes: Isolation of Crystalline 5,12- and 5,7-Diboratapentacene Dianions.

The syntheses, molecular structures, reactivities, and computational assessment of dipotassium diboratapentacene isomers are described (1 and 2). These compounds represent the first examples of aromatized diboraacenes where the boron atoms are spatially separated in different rings of the acene framework. Both 1 and 2 react with carbon dioxide (CO2) via diastereoselective carboxylation of the pentacene backbone that likely proceeds by a frustrated Lewis pair-like mechanism. The placement of the boron atoms and the reactivity studies provide a platform for later stage functionalization of diboraacenes beyond the central ring of the polycyclic aromatic hydrocarbon core.

Advancing racial equity and social justice for Black communities in US tobacco control policy.

The US Food and Drug Administration (FDA) applies the Population Health Standard in tobacco product review processes by weighing anticipated health benefits against risks associated with a given commercial tobacco product at the population level. However, systemic racism (ie, discriminatory policies and practices) contributes to an inequitable distribution of tobacco-related health benefits and risks between white and Black/African Americans at the population level. Therefore, Black-centered, antiracist data standards for tobacco product review processes are needed to achieve racial equity and social justice in US tobacco control policy. Regardless of whether FDA implements such data standards, non-industry tobacco scientists should prioritise producing and disseminating Black-centred data relevant to FDA's regulatory authority. We describe how systemic racism contributes to disparities in tobacco-related outcomes and why these disparities are relevant for population-level risk assessments, then discuss four possible options for Black-centred data standards relevant to tobacco product review processes.

E-cigarette brands and social media influencers on Instagram: a social network analysis.

BACKGROUND: Exposure to visual posts featuring e-cigarette products on social media is associated with increased e-cigarette use among US adolescents. Instagram is the largest source of e-cigarette social media marketing, where influencers-for example, bloggers, brand ambassadors-post promotional materials. This study analysed the network of e-cigarette brands and influencers on Instagram, characterising the most central players in e-cigarette social media marketing. METHODS: We tracked influencers with public profiles on Instagram who posted promotional e-cigarette content in 2020, had over 1000 followers and high user engagement rate (ratio of likes and comments to followers) of 1%-25% per post. By conducting a social network analysis, we identified the most central (highly involved in promotional activities) influencers and e-cigarette brands. The number of the influencers' followers aged 13-17 years old and the age verification practices restricting youth access were also assessed. RESULTS: There is a highly interconnected network of engaging e-cigarette influencers (n=55) worldwide who collaborated with over 600 e-cigarette brands in 2020. The Asian and US influencers had five to six times more teenage followers compared with the European influencers. 75% of the influencers did not restrict youth access to their promotional content on Instagram. The brands Voopotech, Innokin, Geekvape, Lost Vape, Smok and Vaporesso collaborated with the largest number of influencers (mean n=20). CONCLUSIONS: It is important to understand associations among influencers and e-cigarette use behaviours, especially youth, to inform effective public health communication and potential policies that could regulate social media marketing sponsored by e-cigarette companies.

Lucy-Novel Flavored Nicotine Gum, Lozenges, and Pouches: Are They Misleading Consumers?

Background: The packaging and marketing of nicotine gums, lozenges, and pouches can influence users' perceptions about which products are evidence-based for tobacco cessation and which are designed for nicotine maintenance-which could keep people nicotine dependent. Lucy, a company that produces flavored nicotine gums, lozenges, and pouches, could cause confusion by mimicking the packaging of traditional chewing gum and using similar marketing for its approved smoking cessation products and non-approved products. Methods: This commentary describes Lucy's marketing practices that could prolong nicotine dependence rather than aid cessation. Results: Lucy's marketing as "FDA approved for smoking cessation" (true for the lozenges but not the gum or pouches) and "PMTA [Premarket Tobacco Product Application] accepted" could create a false narrative of regulatory acceptance. Its scientific conference presentations could imply that it is endorsed by the scientific community. Its colorful pack design, emphasizing flavors and minimizing nicotine warnings, may attract youth and non-nicotine-users to initiate nicotine use. Conclusion: Lucy's promotion of its products as safe alternatives to other forms of tobacco, its packaging that recalls innocuous chewing gum, and its use of social media to advertise its products should be explored by researchers and considered by policymakers for potential population-level health effects.

A Tale of Two Isomers: Enhanced Antiaromaticity/Diradical Character versus Deleterious Ring-Opening of Benzofuran-fused s-Indacenes and Dicyclopenta[b,g]naphthalenes.

We examine the effects of fusing two benzofurans to s-indacene (indacenodibenzofurans, IDBFs) and dicyclopenta[b,g]naphthalene (indenoindenodibenzofurans, IIDBFs) to control the strong antiaromaticity and diradical character of these core units. Synthesis via 3-functionalized benzofuran yields syn-IDBF and syn-IIDBF. syn-IDBF possesses a high degree of paratropicity, exceeding that of the parent hydrocarbon, which in turn results in strong diradical character for syn-IIDBF. In the case of the anti-isomers, synthesized via 2-substituted benzofurans, these effects are decreased; however, both derivatives undergo an unexpected ring-opening reaction during the final dearomatization step. All the results are compared to the benzothiophene-fused analogues and show that the increased electronegativity of oxygen in the syn-fused derivatives leads to enhancement of the antiaromatic core causing greater paratropicity. For syn-IIDBF increased diradical character results from rearomati-zation of the core naphthalene unit in order to relieve this paratropicity.

Enhancing the Antiaromaticity of s-Indacene through Naphthothiophene Fusion.

Addressing the instability of antiaromatic compounds often involves protection with bulky groups and/or fusion of aromatic rings, thus decreasing paratropicity. We report four naphthothiophene-fused s-indacene isomers, one of which is more antiaromatic than parent s-indacene. This surprising result is examined computationally through nucleus-independent chemical shift XY calculations and experimentally via nuclear magnetic resonance spectroscopy, X-ray crystallography, ultraviolet-visible spectrophotometry, and cyclic voltammetry, with the latter two indicating that this molecule possesses the lowest highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap observed for heterocycle-fused s-indacene.

Categorizing IQOS-Related Twitter Discussions.

(1) Background: The heated tobacco product IQOS, by Philip Morris International, is now available in over 55 countries, including the United States. Social media sites such as Twitter are often used to promote or discuss tobacco products, though prior research has not examined how IQOS is presented on Twitter. (2) Methods: This study collected and categorized Twitter conversations involving IQOS. A manual content analysis was performed on N = 3916 English tweets related to IQOS published internationally between 1 January 2020 and 30 June 2020. (3) Results: Most tweets were either online marketing for IQOS (32.3%) or personal testimonials related to IQOS use (34.2%). Personal testimonial tweets made harm reduction claims about IQOS either as an avenue to quit smoking/tobacco use (3.4%), or in comparison to combustible cigarettes (2.0%). Tobacco policy-related tweets were detected (13.9%), split between discussions of United States (4.9%) and international (4.4%) policies. News media tweets (14.2%) were also detected. (4) Conclusions: Our study suggests IQOS may be understood as a less harmful alternative to vaping and combustible cigarettes. Discussions also suggest IQOS is likely to be used to avoid clean air policies or used in areas in which smoking is restricted.

Impact of eHealth technologies on patient outcomes: a meta-analysis of chronic gastrointestinal illness interventions.

Gastrointestinal (GI) illness interventions are increasingly utilizing eHealth technologies, yet little is currently known about the extent of their impact on patient outcomes. The purpose of this study was to conduct a meta-analysis of the GI eHealth intervention literature. We used a comprehensive search strategy to locate studies. To be included, studies had to be a randomized controlled trial comparing an eHealth intervention condition against a no-treatment or waitlist control condition. Studies had to report data on at least one of the following patient outcomes: medication adherence, quality of life (QoL), psychological distress, illness-related knowledge, or number of patient visits to the clinic/hospital. Analyses weighted effect sizes (d) by their inverse variance and combined them using random effects meta-analytic procedures. K = 19 studies conducted in eight countries with a cumulative sample size of N = 3,193 were meta-analyzed. Findings indicated that GI eHealth interventions improved patients' QoL (d = .25, p = .008), psychological distress (d = .24, p = .017), medication adherence (d = .17, p = .014), and illness-related knowledge (d = .19, p = .002). GI eHealth interventions also significantly reduced the number of patient visits to the clinic/hospital (d = .78, p = .005). Our findings suggest that eHealth interventions hold promise in improving patient outcomes for those with GI illnesses. We suggest the next generation of GI interventions continue developing and evaluating the impact of technology using randomized controlled trial designs, and perhaps consider adapting existing efficacious interventions for burgeoning platforms, such as smartphones and tablets.

Monoradicals and Diradicals of Dibenzofluoreno[3,2-b]fluorene Isomers: Mechanisms of Electronic Delocalization.

The preparation of a series of dibenzo- and tetrabenzo-fused fluoreno[3,2-b]fluorenes is disclosed, and the diradicaloid properties of these molecules are compared with those of a similar, previously reported series of anthracene-based diradicaloids. Insights on the diradical mode of delocalization tuning by constitutional isomerism of the external naphthalenes has been explored by means of the physical approach (dissection of the electronic properties in terms of electronic repulsion and transfer integral) of diradicals. This study has also been extended to the redox species of the two series of compounds and found that the radical cations have the same stabilization mode by delocalization that the neutral diradicals while the radical anions, contrarily, are stabilized by aromatization of the central core. The synthesis of the fluorenofluorene series and their characterization by electronic absorption and vibrational Raman spectroscopies, X-ray diffraction, SQUID measurements, electrochemistry, in situ UV-vis-NIR absorption spectroelectrochemistry, and theoretical calculations are presented. This work attempts to unify the properties of different series of diradicaloids in a common argument as well as the properties of the carbocations and carbanions derived from them.

Late-Stage Modification of Electronic Properties of Antiaromatic and Diradicaloid Indeno[1,2-b]fluorene Analogues via Sulfur Oxidation.

The ability to alter optoelectronic and magnetic properties of molecules at a late stage in their preparation is in general a nontrivial feat. Here, we report the late-stage oxidation of benzothiophene-fused indacenes and dicyclopentanaphthalenes to their corresponding sulfone derivatives. We find that while such modifications increase the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap to a small degree, other properties such as HOMO and LUMO energy levels, molecule paratropicity, and singlet-triplet energy gaps are influenced to a greater degree. The most surprising finding is a change of the bond alternation pattern within the s-indacene core of the sulfones. Computations corroborate the experimental findings and offer plausible explanations for these changes in molecular properties.

Pictorial Cigarette Pack Warnings Increase Some Risk Appraisals But Not Risk Beliefs: A Meta-Analysis.

Pictorial warnings on cigarette packs motivate smokers to quit, and yet the warnings' theoretical mechanisms are not clearly understood. To clarify the role that risk appraisals play in pictorial warnings' impacts, we conducted a meta-analysis of the experimental literature. We meta-analyzed 57 studies, conducted in 13 countries, with a cumulative N of 42,854. Pictorial warnings elicited greater cognitive elaboration (e.g., thinking about the risks of smoking; d = 1.27; p < .001) than text-only warnings. Pictorial warnings also elicited more fear and other negative affect (d = .60; p < .001). In contrast, pictorial warnings had no impact on perceived likelihood of harm (d = .03; p = .064), perceived severity (d = .16; p = .244), or experiential risk (d = .06; p = .449). Thus, while pictorial warnings increase affective and some cognitive risk appraisals, they do not increase beliefs about disease risk. We discuss the role of negative affect in warning effectiveness and the implications for image selection and warning implementation.

Does Perceived Message Effectiveness Predict the Actual Effectiveness of Tobacco Education Messages? A Systematic Review and Meta-Analysis.

Target audience ratings of the likely impact of persuasive messages, known as perceived message effectiveness (PME), are commonly used in health communication campaigns. However, applications of PME rely on a critical assumption-that is, that PME is a valid indicator of the likely effectiveness of messages. To examine the evidence supporting this assumption, we conducted a systematic review and meta-analysis of longitudinal studies in the tobacco education campaigns literature. Six longitudinal studies examining the predictive validity of PME met inclusion criteria. Results indicated that PME ratings were significantly associated with the majority of outcomes studied. In fact, each of the six studies found PME to be associated with at least one outcome, and across the six studies, PME was associated with message recall, conversations about ads, beliefs about smoking and quitting smoking, quit intentions, and cessation behavior. Meta-analyses demonstrated that PME predicted quit intentions (r = .256, p < .001) and cessation behavior (r = .201, p < .001), revealing effects that were small to medium in magnitude. Our results suggest that PME provides some predictive value as to the likely effectiveness of messages, although additional work using different validation designs, with other health behaviors, and among other populations is needed.

Molecule Isomerism Modulates the Diradical Properties of Stable Singlet Diradicaloids.

Inclusion of quinoidal cores in conjugated hydrocarbons is a common strategy to modulate the properties of diradicaloids formed by aromaticity recovery within the quinoidal unit. Here we describe an alternative approach of tuning of diradical properties in indenoindenodibenzothiophenes upon anti → syn isomerism of the benzothiophene motif. This alters the relationship of the S atom with the radical center from linear to cross conjugation yet retains the same 2,6-naphtho conjugation pattern of the rearomatized core. We conduct a full comparison between the anti and syn derivatives based on structural, spectroscopic, theoretical, and magnetic measurements, showing that these systems are stable open-shell singlet diradicaloids that only access their triplet state at elevated temperatures.

Topic Clustering of E-Cigarette Submissions Among Reddit Communities: A Network Perspective.

E-cigarette use in the United States has significantly grown in recent years. Widespread diffusion of e-cigarette content across social media communities may be contributing to this growth. In this study, we (1) explored topics related to e-cigarettes and vaping on Reddit and (2) examined the extent to which these topics clustered across distinct communities. We analyzed a total of N = 79,783 Reddit submissions posted between March 2017 and February 2018 that mentioned at least one e-cigarette or vaping keyword. We created a dictionary to classify submissions into seven different topics related to e-cigarettes and vaping. Submissions were also categorized into one of six mutually exclusive communities identified using subreddit meta-data. Our results indicate that e-cigarette and vaping content on Reddit is primarily about the buying and selling of e-cigarette products. Other common topics included how to build vaping devices, e-juice, and e-cigarette advice. Network correlation analyses found that the distribution of our seven identified topics varied significantly among general e-cigarette, drugs, and research/news subreddit communities. Findings from this study add to a growing literature investigating e-cigarettes and vaping on social media and also contribute to network-level theories by linking communities on Reddit to the diffusion of various depictions of e-cigarettes and vaping.

E-Cigarette Outcome Expectancies among Nationally Representative Samples of Adolescents and Young Adults.

Objectives: We conducted nationally representative surveys of adolescents and young adults to examine associations between e-cigarette outcome expectancies and e-cigarette use. Background: E-cigarette use among adolescents and young adults has grown rapidly in recent years, yet little research has examined the beliefs that may underlie this behavior among nationally representative samples. Methods:N = 1,298 adolescents (13-17) and 2,219 young adults (18-25) were surveyed using a probability-based web panel. Participants completed a survey that included a new outcome expectancy measure examining 3 positive (enjoyment, social influences, advantage over cigarettes) and 2 negative (health concerns, smoker association) expectancy domains and ever having used e-cigarettes [ever use]. Results: Confirmatory factor analyses demonstrated a good fit of the outcome expectancies' factor structure to the data. All outcome expectancies were associated with e-cigarette use in both populations in univariate analyses. In multiple logistic regression models controlling for several covariates, higher expected enjoyment was positively associated with a greater likelihood of e-cigarette use (aOR = 2.10, p < .05) among adolescents. Among young adults, enjoyment (aOR = 3.08, p < .001) was positively associated with a greater likelihood of use while both health concerns (aOR = 0.70, p < .01) and smoker association (aOR = 0.73, p < .05) were negatively associated with e-cigarette use. Conclusions: This study suggests that expected enjoyment is robustly associated with e-cigarette use among both adolescents and young adults. Health concerns may also play a role in e-cigarette use. Implications for e-cigarette prevention efforts and future research directions are discussed.

Exploiting the Hydrogen Bond Donor/Acceptor Properties of PN-Heterocycles: Selective Anion Receptors for Hydrogen Sulfate.

We describe two novel hybrid receptors combining a phosphorus-/nitrogen-containing (PN) phosphonamidate heterocycle with urea recognition units in an arylethynyl backbone. Structural, spectroscopic and computational studies reveal that the origin of superior binding for hydrogen sulfate (HSO4- ) anion is correlated with the formation of strong hetero-complementary hydrogen bonds with the phosphonamidate motif. We further demonstrate that the hybrid host system is capable of capturing/transporting the HSO4- anion from an aqueous, biphasic system.

Serendipitous Rediscovery of the Facile Cyclization of Z,Z-3,5-Octadiene-1,7-diyne Derivatives to Afford Stable, Substituted Naphthocyclobutadienes.

The serendipitous isolation of very small amounts of two naphthocyclobutadiene (NCB) derivatives has led to the computational re-examination of the electrocyclization of Z,Z-3,5-octadiene-1,7-diyne as well as the experimental and computational study of diethynylindeno[2,1-a]fluorene derivatives that contain the 3,5-octadiene-1,7-diyne motif as part of a larger π-framework. In both cases the calculated potential energy surface strongly implicates two successive electrocyclic reactions to afford the antiaromatic products. With the octadienediyne fragment locked in the reactive conformation, the postulated diethynylindeno[2,1-a]fluorene intermediates afford the NCBs in modest to good yields. X-ray crystallography of four NCBs as well as NICS-XY scan calculations show that the paratropic motif is located primarily in the benzocyclobutadiene fragment within the larger π-scaffold.